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The mechanism of cumene peroxidation catalyzed by cobalt(II)-chelated copolymer

机译：钴（II）螯合共聚物催化枯烯过氧化机理

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摘要

Cumene peroxide is an important oxidant in the chemistry industry; however, the conversion and selectivity of cumene peroxide are still not desirable in the practical preparation process because there are some side reactions occurring in the high conversion. Hence, the reaction mechanism is investigated by many researchers. Fortunately, the high catalysis performance polymeric catalyst for cumene peroxidation was successfully synthesized in a previous study, thus, the reaction mechanism is to be investigated in this study. Except for cumene peroxide, three by-products, including acetophenone, 2-phenyl-2-propanol, 1-methylethenyl benzene of cumene peroxidation are identified from the results of high performance liquid chromatography (HPLC), gas chromatography mass spectroscopy (GC-MS), H{sup}1-NMR analysis. Furthermore, the mechanism of cumene peroxidation catalyzed by cobalt(II)-chelated copolymer is also proposed herein. The initiation rate equation represents r{sub}i = k[cumeneK{sup}1.0[polymer-Co(II) complex]{sup}0.5 according to the kinetic study of cumene peroxidation catalyzed by metal-chelated copolymer. Meanwhile, the activation energy of cumene peroxidation by metal-chelated copolymer catalyst is 10.7 kcal/mol, which is located in the range of radical reactions.
机译：异丙苯过氧化物是化学工业中的重要氧化剂。然而，在实际的制备过程中，过氧化枯烯的转化率和选择性仍然不理想，因为在高转化率中会发生一些副反应。因此，许多研究者对反应机理进行了研究。幸运的是，在先前的研究中成功地合成了高催化性能的枯烯过氧化聚合催化剂，因此，该反应机理有待研究。从高效液相色谱（HPLC），气相色谱质谱（GC-MS）的结果中鉴定出除了过氧化枯烯以外，还发现了苯乙酮，2-苯基-2-丙醇，1-甲基乙烯基苯等异丙苯过氧化的三种副产物。 ），H {sup} 1-NMR分析。此外，本文还提出了钴（II​​）-螯合共聚物催化的枯烯过氧化机理。根据金属螯合共聚物催化的枯烯过氧化反应的动力学研究，引发速率方程表示r {sub} i = k [cumeneK {sup} 1.0 [聚合物-Co（II）配合物] {sup} 0.5”。同时，金属螯合共聚物催化剂的枯烯过氧化活化能为10.7 kcal / mol，处于自由基反应范围内。

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